KR100336618B1 - New metallocene compounds containing amine substituted organosilane - Google Patents

Abstract

The present invention relates to a novel metallocene compound crosslinked with a dialkylsilyl group having the formula (1), which compound is used for polymer polymerization.

N in Formula 1 is 0 or 1; Cp is cyclopentadienyl, indenyl or fluorenyl; Two R's are linked by a ring bond by -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , or one of the two Rs is alkyl of C ₁ -C ₆ The other is R ¹ ₃ Si (CH ₂ ) _m, or two R are both R ¹ ₃ Si (CH ₂ ) _m , wherein R ¹ is C ₁ -C ₆ alkyl, m is 2-5 An integer; M represents Zr, Ti or Hf.

Description

Novel metallocene compounds including amine-substituted organosilanes {NEW METALLOCENE COMPOUNDS CONTAINING AMINE SUBSTITUTED ORGANOSILANE}

The present invention relates to novel metallocene compounds, including organosilanes substituted with amine groups.

Since the low pressure polymerization of olefins using transition metals was developed by Ziegler and Natta for the first time in the 1950s, various polymer catalysts have been studied. Recently, research on polymer synthesis using metallocene catalysts has been actively conducted. These polymers are attracting attention because of their commercial utility in various fields such as petroleum and fiber. Especially, asymmetric metallocene catalyst compounds using Group 4 transition metals and two cyclopentadienyl groups as ligands have been used in polymer polymerization. As polymer-selective polymers can be converted into stereoselective polymers, which were difficult to control in polymer polymerization, researches are being actively conducted due to the advantage of selectively synthesizing different polymer arrays under the same polymer polymerization conditions [ Organometallics , 12 , 4391 (1993). Of the numerous metallocene compounds known to date, ansa metallocene compounds, in which two ligands coordinated to a transition metal are bridged to each other by carbon or other molecules, are used as a catalyst in polymer polymerization. It has been reported that polymers having stereoscopic orientations different from those in which no bonds are formed, and polymers having different orientations, are synthesized depending on the compounds used for bridging [ J. Organomet . Chem ., 489 , 29-34 (1995). It is also known that the use of ansa metallocene catalysts having a cyclopentadiene ring in olefin polymerization can selectively obtain α-olefin polymers among various stereoalignments [US Pat 5,055,438; Chem . Abstr ., 118 , 60,238 (1993). Among the ansa metallocene catalysts having a cyclopentadiene ring, metallocene catalysts having a ligand of amido-cyclopentadiene have a higher Lewis acid effect than a catalyst having only cyclopentadiene, which is known to be more active as a catalyst in polymer polymerization. [ J. Am. Chem. Soc. , 116 , 4623 (1994). An 1995 anza metallocene compound catalyst was reported using fluorene instead of cyclopentadiene in a ligand and in which fluorenyl and amine groups are crosslinked with dimethylsilane [ Organometallics , 14 , 789 (1995); J. Organomet . Chem. , 508 , 91 (1996)], this metallocene catalyst is known as a compound useful for synthesizing homo-arranged polypropylene when used with methylaluminoxane (MAO) as a cocatalyst during propylene polymerization [US Pat 5,055,438; Chem . Abstr . 118 , 60,238 (1993)]. However, when the dimethylsilyl group is used for the bridge bond, the ring is easily broken during the synthesis of the metallocene compound, which is difficult to synthesize.

Accordingly, the present invention has been made to solve the above problems, and to provide a new form of ansa metallocene compound having a cyclopentadiene ring and an amine group, and substituted various functional groups in the silyl group. do.

The present inventors have succeeded in synthesizing a novel metallocene compound having the formula (1) below.

[Formula 1]

N in Formula 1 is 0 or 1; Cp is cyclopentadienyl, indenyl or fluorenyl; Two R's are linked by a ring bond by -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -or one of the two R is alkyl of C ₁ -C ₆ The other is R ¹ ₃ Si (CH ₂ ) _m, or two R are both R ¹ ₃ Si (CH ₂ ) _m , wherein R ¹ is C ₁ -C ₆ alkyl, m is 2-5 An integer; M represents Zr, Ti or Hf.

Examples of C ₁ -C ₆ alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, t-butyl, n-pentyl, hexyl and the like.

Examples of R ¹ are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, and the like. , Preferably methyl, ethyl, propyl, isopropyl, most preferably methyl.

_M in the formula R ¹ ₃ Si (CH ₂ ) _m has 2-5, preferably 2-4, most preferably m = 2.

The compound of Formula 1 of the present invention was synthesized by reacting an organosilane compound substituted with a (tertiary-butyl) amino group having Formula 2 with a chloride of a Group IV transition metal having Formula 3. Formulas 2 and 3 and Scheme 1 are as follows.

[Formula 2]

[Formula 3]

MCl ₄

The definitions of n, Cp, R and M in Chemical Formulas 2 and 3 and Scheme 1 are the same as those in Chemical Formula 1.

Referring to the manufacturing method of the present invention in more detail as follows.

Scheme 2 below shows an example of the synthesis of the compound having the formula (2) as an intermediate.

Among the various substituents, silacyclopentane or silacyclohexyl is subjected to Grignard reaction of metal magnesium with 1,4-dichlorobutane (n = 1) or 1,5-dichloropentane (n = 2) in an ether solvent. It was synthesized by reacting with chloromethyltrichlorosilane. Reaction of the synthesized compound with LiNH ^t Bu [ J. Organomet . Chem ., 190 , 1 (1980)] and reaction with CpLi (where Cp means cyclopentadiene, indene or fluorene) [ Journal of Polymer Science : Part A: Polymer Chem . 32 , 149-158 (1994)], to prepare a silacyclopentane compound substituted with an amido group and a cyclopentadiene group.

However, in the case of the organic silane compound in which another silyl functional group is added to the silane and the fluorenyl group is substituted, such a method is difficult to synthesize. Therefore, the present inventors synthesized using a method of synthesizing a silane compound substituted with a fluorenyl group using a biphenyl derivative and a dichloroalkylsilane compound recently developed (US Pat 5,847,182). Using a silane compound substituted with a fluorenyl group synthesized by this method, a compound having an amido group and a fluorenyl group substituted through the reaction route shown in Scheme 3 below, and to which silane groups are added Synthesized.

Fluorinated silane compounds substituted with fluorene rings were substituted for hydrogen by chlorine using the well-known method LiAlH ₄ ( The chemistry of organic silicon compounds , Jone Wiley & Sons, 1989, 30-31). Platinum catalysts widely used in the reaction [ Organometallics , 6 , 191 (1987)] were optionally substituted with hydrogen silyl groups. The remaining hydrogen was replaced with chlorine using copper chloride [ Organometallics , 11 , 2708 (1992)]. Using normal butyllithium, the substituted chlorine is reacted with t-butylamine [ J. Organomet . Chem ., 190 , 1 (1980)] A silane compound substituted with a fluorenyl group and an amido group was synthesized. In this reaction, the silylalkyl group substituting hydrogen is represented by CH ₂ = CH- (CH ₂ ) _n SiR ¹ ₃ , where n is an integer of 0-4 and R ¹ is as defined above.

The reaction for synthesizing the metallocene compound of Chemical Formula 1 is the same as in Scheme 1, and a specific embodiment thereof is as follows. That is, the compound of formula 2 was lithiated using normal butyllithium under nitrogen atmosphere, and ZrCl ₄ , a chloride of Group 4 transition metal, was slowly added at -78 ° C. Lithium chloride produced after the reaction was removed using toluene, and recrystallized at -10 ℃ using toluene and pentane to obtain a metallocene compound of formula (1). In this example ZrCl ₄ is replaceable with TiCl ₄ or HfCl ₄ .

The following examples will illustrate the invention in more detail, but the scope of the invention is not limited thereto.

Example 1

Reaction of 9-[[(1,1-dimethylethyl) amino] -di (2-trimethylsilylethyl) silyl] methyl] -9H-fluorene with zirconium tetrachloride

In a 100 ml two-necked round bottom flask, 1.86 g (3.87 mmol) of 9-[[(1,1-dimethylethyl) amino] -di (2-trimethylsilylethyl) silyl] methyl] -9H-fluorene and 50 ml of ether While stirring at 0 ° C., 2.97 ml (7.74 mmol) of 2 mol of normal butyllithium was slowly added for 10 minutes, and then the reaction was heated to room temperature for 4 hours. The reaction was then lowered to -78 ° C using dry ice and acetone, and then 0.959 g (4.11 mmol) of solid zirconium tetrachloride were added. The mixture was stirred at −78 ° C. for 1 hour, and the temperature was raised to room temperature, followed by stirring for 1 day. The ether was removed using a vacuum pump, and then toluene was added thereto to precipitate lithium chloride, followed by filtration. The filtrate was concentrated to about 5 ml and slowly added dropwise 20 ml of pentane and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas to dichloro [N- (1,1-dimethylethyl) -1-[[4a, 4b, 8a, 9,9a-η) -9H-fluorene-9- Neil] methyl] -1,1-di (2-silylethyl) silaamito-N] zirconium 0.61 g was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.138 (s, 18H, SiCH ₃ ), 0.84-1.016 (m, 8H, SiCH ₂ ), 1.35 (s, 9h, ^t Bu), 2.74 (s, 2H, CH ₂ ), 7.15-7.78 (m, 8H, C ₁₃ H ₈ )

Example 2

Reaction of 9-[[(1,1-dimethylethyl) amino] -di (2-trimethylsilylethyl) silyl] methyl] -9H-fluorene with titanium tetrachloride

In a 100 ml two-necked round bottom flask, 1.8 g (3.74 mmol) of 9-[[((1,1-dimethylethyl) amino] -di (2-trimethylsilylethyl) silyl] methyl] -9H-fluorene and 50 ml of toluene While stirring at 0 ° C., 2.87 ml (7.48 mmol) of normal butyllithium was slowly added for 10 minutes, and the reaction was heated to room temperature to react for 4 hours. The reaction was then lowered to -78 ° C using dry ice and acetone, and then 1.38 g (4.11 mmol) of solid titanium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. After precipitation of lithium chloride, the filtrate was concentrated to about 5 ml, 20 ml of pentane was slowly added dropwise and refrigerated at -35 ° C to precipitate the reaction. The precipitate was filtered through a glass filter system in a glove box under argon gas, and 0.27 g of dichloro [N- (1,1-dimethylethyl) -1-[[(4a, 4b, 8a, 9,9a-η) -9H-flu Oren-9-yl] methyl] -1,1-di (2-silylethyl) silylamito-N] titanium.

¹ H-NMR (C ₆ D ₆ ) δ = 0.14 (s, 18H, SiCH ₃ ), 0.80-1.02 (m, 8H, SiCH ₂ ), 1.31 (s, 9h, ^t Bu), 2.80 (s, 2H, CH ₂ ), 7.12-7.90 (m, 8H, C ₁₃ H ₈ )

Example 3

Reaction of 9-[[(1,1-dimethylethyl) amino] -di (3-trimethylsilylpropyl) silyl] methyl] -9H-fluorene with zirconium tetrachloride

2.78 g (5.8 mmol) of 9-[[(1,1-dimethylpropyl) amino] -di (2-trimethylsilylethyl) silyl] methyl] -9H-fluorene and 70 ml of ether in a 100 ml two-necked round bottom flask After stirring at 0 ° C., 4.3 ml (11.6 mmol) of 2 mol of normal butyllithium (2.67 N) was slowly added for 10 minutes, and the reaction was allowed to react at room temperature for 4 hours. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 1.35 g (5.8 mmol) of solid zirconium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. The ether was removed using a vacuum pump, and then toluene was added thereto to precipitate lithium chloride, followed by filtration. The filtrate was concentrated to about 5 ml and slowly added dropwise 20 ml of pentane and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas to dichloro [N- (1,1-dimethylethyl) -1-[[(4a, 4b, 8a, 9,9a-η) -9H-fluorene-9 -Nyl] methyl] -1,1-di (2-silylpropyl) silaamito-N] zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = -0.05 (s, 18H, SiCH ₃ ), 0.37 (t, 8H, SiCH ₂ ), 1.20 (m, 4H, CH ₂ ), 1.35 (s, 9h, ^t Bu), 2.74 (s, 2H, CH ₂ ), 7.27-7.77 (m, 8H, C ₁₃ H ₈ )

Example 4

Reaction of 9-[[(1,1-dimethylethyl) amino] -di (3-trimethylsilylpropyl) silyl] methyl] -9H-fluorene with titanium tetrachloride

In a 100 ml two-necked round-bottom flask, 2.95 g (6.10 mmol) of 9-[[(1,1-dimethylpropyl) amino] -di (3-trimethylsilylpropyl) silyl] methyl] -9H-fluorene and 70 ml of toluene After stirring at 0 ° C., 4.6 ml (12.3 mmol) of 2 mol of normal butyllithium (2.67 N) was slowly added for 10 minutes, and the reaction was allowed to react at room temperature for 4 hours. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 2.05 g (6.1 mmol) of solid titanium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. After precipitation of lithium chloride, the filtrate was concentrated to about 5 ml, 20 ml of pentane was slowly added dropwise and refrigerated at -35 ° C to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas and 1.3 g of dichloro [N- (1,1-dimethylethyl) -1-[[(4a, 4b, 8a, 9,9a-η) -9H-flu Oren-9-yl] methyl] -1,1-di (3-silylpropyl) silaamito-N] titanium.

¹ H-NMR (C ₆ D ₆ ) δ = 0.08 (s, 18H, SiCH ₃ ), 0.40 (t, 8H, SiCH ₂ ), 1.20 (m, 4H, CH ₂ ), 1.30 (s, 9H, ^t Bu ), 2.74 (s, 2H, CH ₂ ), 7.26-7.78 (m, 8H, C ₁₃ H ₈ )

Example 5

9-[(1,1-dimethylethyl) amino]-(2-trimethylsilylethyl) methylsilyl] -9H-fluorene with zirconium tetrachloride +

In a 100 ml two-necked round bottom flask, 3.9 g (10.2 mmol) of 9-[(1,1-dimethylethyl) amino]-(2-trimethylsilylethyl) methylsilyl] -9H-fluorene and 70 ml of ether were heated to 0 ° C. 7.65 ml (20.4 mmol) of normal butyllithium was slowly added while stirring at. The reaction was heated to room temperature and reacted for 4 hours. The reaction was then lowered to -78 ° C using dry ice and acetone, and then 2.56 g (11.0 mmol) of solid zirconium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. The ether was removed using a vacuum pump, and then toluene was added thereto to precipitate lithium chloride, followed by filtration. The filtrate was concentrated to about 5 ml and slowly added dropwise 20 ml of pentane and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas and 1.9 g of dichloro [N- (1,1-dimethylethyl) -1-[(4a, 4b, 8a, 9,9a-η) -9H-fluorene -9-yl] -1- (2-trimethylsilylethyl) methylsilaamito-N] zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.16 (s, 9H, SiCH ₃ ), 0.83 (s, 3H, SiCH ₃ ), 1.07-1.14 (m, 4H, SiCH ₂ ), 1.31 (s, 9H, ^t Bu), 7.20-7.91 (m, 8H, C ₁₃ H ₈ )

Example 6

Reaction of 9-[(1,1-dimethylethyl) amino]-(2-trimethylsilylethyl) methylsilyl] -9H-fluorene with titanium tetrachloride

In a 100 ml two-necked round bottom flask, 2.0 g (5.1 mmol) of 9-[(1,1-dimethylethyl) amino]-(2-trimethylsilylethyl) methylsilyl] -9H-fluorene and 70 ml of toluene were 0 ° C. 3.9 ml (10.4 mmol) of normal butyllithium were slowly added while stirring at. The reaction was heated to room temperature and reacted for 4 hours. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 1.75 g (5.2 mmol) of solid titanium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. After filtering the lithium chloride, the filtrate was concentrated to about 5 ml and slowly added dropwise 20 ml of pentane and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas and 0.78 g of dichloro [N- (1,1-dimethylethyl) -1-[(4a, 4b, 8a, 9,9a-η) -9H-fluorene -9-yl] -1- (2-trimethylsilylethyl) methylsilamito-N] titanium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.16 (s, 9H, SiCH ₃ ), 0.83 (s, 3H, SiCH ₃ ), 1.07-1.14 (m, 4H, SiCH ₂ ), 1.31 (s, 9H, ^t Bu), 7.20-7.91 (m, 8H, C ₁₃ H ₈ )

Example 7

Reaction of 9-[(1,1-dimethylethyl) amino]-(3-trimethylsilylpropyl) methylsilyl] -9H-fluorene with zirconium tetrachloride

In a 100 ml two-necked round bottom flask, 0.62 g (1.57 mmol) of 9-[(1,1-dimethylethyl) amino]-(3-trimethylsilylpropyl) methylsilyl] -9H-fluorene and 60 ml of ether were heated to 0 ° C. 1.2 ml (3.14 mmol) of normal butyllithium were slowly added while stirring at. The reaction was heated to room temperature and reacted for 4 hours. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 0.44 g (1.8 mmol) of solid zirconium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. The ether was removed using a vacuum pump, and then toluene was added thereto to precipitate lithium chloride, followed by filtration. The filtrate was concentrated to about 5 ml and slowly added dropwise 20 ml of pentane and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas and 0.5 g of dichloro [N- (1,1-dimethylethyl) -1-[(4a, 4b, 8a, 9,9a-η) -9H-fluorene -9-yl] -1- (3-trimethylsilylpropyl) methylsilaamito-N] zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = -0.09 (s, 9H, SiCH ₃ ), 0.02 (s, 2H, SiCH ₃ ), 0.35 (m, 2H, CH ₂ ), 0.80 (s, 3H, SiCH ₃ ), 1.08-1.11 (m, 2H, SiCH ₃ ), 1.25 (s, 9H, ^t Bu), 7.20-7.91 (m, 8H, C ₁₃ H ₈ )

Example 8

Reaction of 9-[(1,1-dimethylethyl) amino]-(3-trimethylsilylpropyl) methylsilyl] -9H-fluorene with titanium tetrachloride

In a 100 ml two-necked round bottom flask, 0.68 g (1.57 mmol) of 9-[(1,1-dimethylethyl) amino]-(3-trimethylsilylpropyl) methylsilyl] -9H-fluorene and 70 ml of toluene were 0 ° C. 1.2 ml (3.14 mmol) of normal butyllithium were slowly added while stirring at. The reaction was heated to room temperature and reacted for 4 hours. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 0.63 g (1.9 mmol) of solid titanium tetrachloride were added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. After filtering the lithium chloride, the filtrate was concentrated to about 5 ml, 20 ml of pentane was slowly added dropwise and refrigerated at -35 ℃ to precipitate the reaction. The precipitate was filtered through a glass filter in a glove box under argon gas to remove 0.4 g of dichloro [N- (1,1-dimethylethyl) -1-[(4a, 4b, 8a, 9,9a-η) -9H-fluorene -9-yl] -1- (3-trimethylsilylpropyl) methylsilaamito-N] titanium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.0 (s, 9H, SiCH ₃ ), 0.02 (s, 2H, SiCH ₃ ), 1.30 (m, 2H, CH ₂ ), 0.80 (s, 3H, SiCH ₃ ), 1.08-1.13 (m, 2H, SiCH ₂ ), 1.30 (s, 9H, ^t Bu), 7.21-7.89 (m, 8H, C ₁₃ H ₈ )

Example 9

Reaction of [(1,1-dimethylethyl) amino] -silacyclopentyl] methyl-cyclopentadiene with zirconium tetrachloride

In a 100 ml two-necked round-bottom flask, 1.2 g (5.1 mmol) of [[(1,1-dimethylethyl) amino] silacyclopentyl] methyl] cyclopentadiene and 50 ml of ether were stirred at 0 ° C. and normal butyllithium 4.0 ml (10.0 mmol) were added slowly. The reaction was heated to room temperature and reacted for one day. In another 100 ml round bottom flask, 1.2 g (5.1 mmol) of solid zirconium tetrachloride was dissolved in ether, lowered to -78 ° C using dry ice and acetone, and the reaction was added dropwise. Stirred at -78 ℃ for 1 hour and warmed to room temperature and stirred for one day. The ether was removed in vacuo and again 30 ml of toluene was added to filter lithium chloride. The filtrate was concentrated to about 5 ml and refrigerated at -20 ° C to precipitate the reaction. The precipitate was filtered through a glove box under argon gas and 0.3 g (15%) of dichloro [N- (1,1-dimethylethyl)-(cyclopentadienyl) methyl)-(silacyclopentyl) silamito-N] Zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.59-1.0 (m, 4H, SiCH ₂ ), 1.51 (s, 9H, ^t Bu), 1.4 (m, 4H, CH ₂ ), 1.71 (s, 2H, CH ₂ ), 5.80 (s, 1H, CH) 6.20 (s, 1H, CH), 7.16 (s, 2H, CH).

Example 10

Reaction of [[(1,1-dimethylethyl) amino] -silacyclopentyl] methyl] -1H-indene with zirconium tetrachloride

In a 100 ml two-necked round-bottom flask, 2.0 g (7.2 mmol) of [[(1,1-dimethylethyl) amino] silacyclopentyl] methyl] -1H-indene and 50 ml of ether were stirred at 0 ° C. with normal butyllithium 5.7 ml (14.3 mmol) was slowly added dropwise and the reaction was allowed to react at room temperature for one day. In another 100 ml flask, 1.77 g (7.6 mmol) of solid zirconium tetrachloride was dissolved in ether, and then cooled to -78 ° C using dry ice and acetone, and the reaction was added dropwise. After dropping, the mixture was stirred for 1 hour at -78 ° C, and the temperature was raised to room temperature, followed by stirring for one day. The ether was removed in vacuo and again 30 ml of toluene was added to filter lithium chloride, the filtrate was concentrated to about 5 ml and refrigerated at -20 ° C to precipitate the reaction. The precipitate was filtered through a glove box under argon gas to give 0.5 g (16%) of dichloro [N- (1,1-dimethylethyl) -1-[[(1,2,3,8,9-η) -1H- Inden-1-yl] methyl]-(silacyclopentyl) silaamido-N] zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.71-1.77 (m, 4H, SiCH ₂ ), 1.06 (m, 4H, CH ₂ ), 1.40 (s, 9H, ^t Bu), 2.10 (s, 2H, CH ₂ ), 6.18 (d, 1H, CH) 6.41 (d, 1H, CH), 6.99-7.30 (m, 4H, C ₆ H ₄ )

Example 11

Reaction of 9-[[(1,1-dimethylethyl) amino] -silacyclopentyl] methyl-9H-fluorene with zirconium tetrachloride

In a 100 ml two-necked round bottom flask, 2.54 g (7.6 mmol) of 9-[[(1,1-dimethylethyl) amino] silacyclopentyl] methyl] -9H-fluorene and 50 ml of ether were stirred at 0 ° C. 6.2 ml (17.0 mmol) of normal butyllithium were slowly added. The reaction was heated to room temperature and reacted for one day. The reaction was then cooled to -78 ° C using dry ice and acetone, and then 1.77 g (7.6 mmol) of solid zirconium tetrachloride were dissolved in ether and added. Stirred at -78 ° C for 1 hour and the temperature was raised to room temperature and stirred for one day. The ether was removed in vacuo, and 30 ml of toluene was added again to filter lithium chloride. The filtrate was concentrated to about 5 ml, and 20 ml of pentane was slowly added dropwise and refrigerated at -35 ° C to precipitate the reaction. The precipitate was filtered through a glove box under argon gas to yield 0.8 g (21%) of dichloro [N- (1,1-dimethylethyl) -1-[[(4a, 4b, 8a, 9,9a-η) -9H- Fluorene-9-yl] methyl]-(silacyclopentyl) silaamido-N] zirconium was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.86-0.93 (m, 4H, SiCH ₂ ), 1.27 (s, 9H, ^t Bu), 1.62 (m, 4H, CH ₂ ), 2.50 (s, 2H, CH ₂ ), 7.14-7.73 (m, 8H, C ₁₃ H ₈ ).

As described above, a new type of ansa metallocene compound having a cyclopentadiene ring and an amine group and having substituted various functional groups in the silyl group was easily synthesized.

Claims (2)

Metallocene compounds of novel organosilane derivatives represented by the following formula (I): (I) In the above formula (I), n is 0 or 1; Cp is cyclopentadienyl, indenyl or fluorenyl; Two R's are linked by a ring bond by -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -or one of the two R is methyl and the other is Me ₃ Si (CH ₂ ) _m , or both R are Me ₃ Si (CH ₂ ) _m , where m is 2 or 3; M represents Zr, Ti or Hf. A compound according to claim 1, wherein R is 2- (trimethylsilyl) ethyl or 3- (trimethylsilyl) propyl.